JP4875252B2 - Polycyanoaryl ether and process for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polycyanoaryl ether and a method for producing the same.
[0002]
[Prior art]
Currently, the material revolution is progressing on a global scale, but synthetic polymer materials such as plastics occupy the center, and now surpass metal and inorganic materials in terms of molding, processability and cost. ing.
[0003]
Such plastics are generally general-purpose plastics widely used for daily necessities around us; engineering plastics with even better performance in terms of performance such as mechanical properties and heat resistance; and even higher than this engineering plastic It is classified as a super engineering plastic with the performance of Among these, engineering plastics are high-performance polymer materials that combine heat resistance (continuous use temperature of about 100 ° C or higher) and high mechanical properties (strength, elastic modulus, etc.), such as automobiles, electronic information, precision machinery, etc. As an indispensable material in the industrial field, polyamide (nylon), acetal resin, polycarbonate, polyester and modified polyphenylene ether are called five major engineering plastics.
[0004]
Super engineering plastics are intended to aim at higher performance than conventional engineering plastics in terms of heat resistance and mechanical properties. Next to conventional general-purpose plastics and engineering plastics, It is attracting attention as a material that plays a role in technological innovation in a wide range of industrial fields such as information, precision machinery and aerospace.
[0005]
This super-engineering plastic has a basic structure of a polymer composed of an aromatic skeleton, and related materials include aramid (aromatic polyamide), polyethersulfone, polyarylate, polyphenylene sulfide, polyetherketone and polyetherimide. Currently, it is being industrialized one after another.
[0006]
On the other hand, aromatic polyether nitriles (PEN) are one of materials expected as super engineering plastics having excellent heat resistance, hydrolysis resistance and weather resistance. These aromatic polyether nitriles (PEN) have a cyano group that is a polar group in addition to the above characteristics, and thus have excellent adhesion to glass fibers and the like, and are used as a matrix for composite materials. However, PEN currently produced has a problem that it is difficult to develop into a film or the like because of poor solubility.
[0007]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a novel industrially versatile polycyanoaryl ether having excellent heat resistance, hydrolysis resistance and weather resistance, and a method for producing the same.
[0008]
Another object of the present invention is to provide a polycyanoaryl ether having improved solubility in addition to the above properties and a method for producing the same.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to overcome the above problems, the present inventors have found that by introducing fluorine atoms into the aromatic polyether nitrile, the cohesive force between the main chains is weakened, thereby imparting solubility. I knew. In addition, since the polycyanoaryl ether obtained in this way has a low polarizability of C—F bond, in addition to the improvement of the above-mentioned various performances, the improvement of transparency and the reduction of hygroscopicity are also achieved. Furthermore, the bond dissociation energy of the C—F bond is larger than that of the C—H bond, and an improvement in heat resistance and radiation resistance can also be expected. It is possible to impart solubility without impairing the properties, and development of a new high-performance material superior to conventional PEN can be expected. In addition, by introducing fluorine atoms, the dielectric constant of the material can be reduced. I also learned that it is possible and expected to be applied as an electronic material.
[0010]
The present invention has been completed based on the above findings.
[0011]
That is, these various objects are achieved by the following (1) to (8).
[0012]
(1) The following formula (1):
[0013]
[Formula 4]
[0014]
However, R ¹ Is an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -12 alkylamino group, optionally substituted alkylthio group having 1 to 12 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, and substituents. Represents a good aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, or an arylthio group having 6 to 20 carbon atoms which may have a substituent. R ² Represents a divalent organic group; and n represents the degree of polymerization.
A polycyanoaryl ether represented by
[0015]
(2) In the formula (1), R ¹ Represents an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and the polycyanoaryl ether according to (1) above.
[0016]
(3) In the formula (1), R ¹ Represents the phenoxy which may have a substituent, The polycyano aryl ether as described in said (2).
[0017]
(4) In the formula (1), R ² Is the following formula:
[0018]
[Chemical formula 5]
[0019]
The polycyanoaryl ether according to any one of (1) to (3), which represents any one of
[0020]
(5) The following formula (2):
[0021]
[Chemical 6]
[0022]
However, R ¹ Is an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and 1 carbon atom which may have a substituent. -12 alkylamino group, optionally substituted alkylthio group having 1 to 12 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, and substituents. Represents an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms which may have a substituent, or an arylthio group having 6 to 20 carbon atoms which may have a substituent ,
A tetrafluorobenzonitrile derivative represented by the following formula (3):
[0023]
[Chemical 7]
[0024]
However, R ² Represents a divalent organic group,
A process for producing a polycyanoaryl ether according to the above (1) or (2), which comprises polymerizing in the presence of a dihydroxy compound and a basic catalyst.
[0025]
(6) The method according to (5) above, wherein the polymerization of the tetrafluorobenzonitrile derivative and the dihydroxy compound is performed at a temperature of 200 ° C. or lower.
[0026]
(7) The method according to (5) or (6), wherein the basic catalyst is at least one selected from the group consisting of potassium carbonate, calcium carbonate, potassium hydroxide, calcium hydroxide, or potassium fluoride.
[0027]
(8) The dihydroxy compound has the following formula:
[0028]
[Chemical 8]
[0029]
The method according to any one of (5) to (7) above, wherein
[0030]
DETAILED DESCRIPTION OF THE INVENTION
The polycyanoaryl ether of the present invention has the following formula (1):
[0031]
[Chemical 9]
[0032]
It is a novel compound shown by these.
[0033]
In the above formula (1), R ¹ Is an optionally substituted alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl and 2-ethylhexyl, preferably methyl, ethyl, propyl and butyl; optionally substituted alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, Propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, furfuryloxy and allyloxy, preferably methoxy, ethoxy, propoxy, i Propoxy and butoxy; optionally substituted alkylamino groups having 1 to 12 carbon atoms such as methylamino, ethylamino, dimethylamino, diethylamino, propylamino, n-butylamino, sec-butylamino and tert -Butylamino, preferably methylamino, ethylamino, dimethylamino and diethylamino; optionally substituted alkylthio groups having 1 to 12 carbon atoms, such as methylthio, ethylthio, propylthio and n-butylthio, sec-butylthio , Tert-butylthio and iso-propylthio, preferably methylthio, ethylthio and propylthio; optionally substituted aryl group having 6 to 20 carbon atoms, such as phenyl, benzyl, phenethyl, o-, m- or p-tolyl, , 3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl and pyrenyl, preferably phenyl and o-, m- and p-tolyl; optionally substituted carbon atoms 6 to 20 aryloxy groups such as phenoxy, benzyloxy, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester and phenyl ester; The same) groups derived from naphthoxy, o-, m- or p-methylphenoxy, o-, m- or p-phenylphenoxy, phenylethynylphenoxy and groups derived from cresotinic acid and its esters, preferably phenoxy and na Ftoxy; optionally substituted arylamino group having 6 to 20 carbon atoms, such as anilino, o-, m- or p-toluidino, 1,2- or 1,3-xylidino, o-, m -Or p-methoxyanilino and a group derived from anthranilic acid and its esters, preferably anilino and o-, m- or p-toluidino; or an optionally substituted arylthio group having 6 to 20 carbon atoms For example, phenylthio, phenylmethanethio, o-, m- or p-tolylthio and groups derived from thiosalicylic acid and its esters, preferably phenylthio. Among these, an aryloxy group, an arylthio group and an arylamino group which may have a substituent are preferable, and further, phenoxy, phenylthio and anilino are R ¹ As the most preferred.
[0034]
In the above formula (1), R ¹ Substituents that can be used to represent an alkyl group, an alkoxy group, an alkylamino group, an alkylthio group, an aryl group, an aryloxy group, an arylamino group, or an arylthio group having a substituent are determined according to the desired characteristics of the target product. Although not particularly limited, for example, an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, Examples include isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl; halogen atoms such as fluorine, chlorine, bromine and iodine; cyano group, nitro group and carboxyester group. Of these, methyl and carboxyester groups are preferred.
[0035]
Further, in the above formula (1), R ² Represents a divalent organic group, and examples thereof include a group represented by the following formula.
[0036]
[Chemical Formula 10]
[0037]
Of these, the following formula:
[0038]
Embedded image
[0039]
The divalent organic group represented by R is R ² As the following formula:
[0040]
Embedded image
[0041]
The divalent organic group represented by R is R ² As preferred.
[0042]
Further, in the above formula (1), n represents the degree of polymerization, specifically 5 to 1000, preferably 10 to 500. The polycyanoaryl ether of the present invention is composed of the same repeating unit of the structural unit of the above formula (1). The Or in the latter case, the repeating unit may be in the form of a block. The Or random.
[0043]
Moreover, although the manufacturing method of the polycyanoaryl ether of this invention is explained in full detail below, the terminal of the polycyanoaryl ether shown by Formula (1) is fluorine on the benzene ring side containing a fluorine atom from this description. , Oxygen atom (R ² ) Side is a hydrogen atom, that is, the polycyanoaryl ether represented by the formula (1) is represented by the following formula (4):
[0044]
Embedded image
[0045]
It is thought that it is a polymer shown by.
[0046]
The polycyanoaryl ether of the present invention has the following formula (2):
[0047]
Embedded image
[0048]
A tetrafluorobenzonitrile derivative represented by the following formula (3):
[0049]
Embedded image
[0050]
It is manufactured by polymerizing in the presence of a basic catalyst and a dihydroxy compound represented by At this time, R in the above formula (2) ¹ And R in the above formula (3) ² Is defined as R in the above formula (1). ¹ And R ² It is the same as the definition of.
[0051]
In the present invention, the tetrafluorobenzonitrile derivative of the formula (2) can be produced by a known method. For example, the formula: R ¹ H [wherein R ¹ Is the same as defined in the above formula (1)] in the presence of a basic compound in an organic solvent in the presence of 2,3,4,5,6-pentafluorobenzonitrile (in the present specification, “ (Also referred to as “PFBN”).
[0052]
In the above reaction, the formula: R ¹ The compound represented by H and PFBN may each be used as a single compound or two or more of the formulas: R ¹ Although it may be used in the form of a mixture of a compound represented by H and / or PFBN, it is preferably used as a single compound in consideration of the purification process and the physical properties of the polymer. In the latter case, the total number of moles of the plural or single PFBN used is the plural or single formula: R ¹ It is preferably equal to or approximately equal to the total number of moles of the compound represented by H. ¹ The amount of the compound represented by H is preferably 0.1 to 5 mol, more preferably 0.5 to 2 mol, relative to 1 mol of PFBN.
[0053]
Examples of the organic solvent that can be used in the above reaction include polar solvents such as N-methyl-2-pyrrolidinone, N, N-dimethylacetamide, acetonitrile, benzonitrile, nitrobenzene, nitromethane, and methanol; and these polar solvents and toluene, Examples thereof include a mixed solvent with a nonpolar solvent such as xylene. These organic solvents may be used alone or in the form of a mixture of two or more. Moreover, the density | concentration of PFBN in an organic solvent is 1-40 mass%, Preferably, it is 5-30 mass%. In this case, when toluene or other similar solvent is used in the initial stage of the reaction, water produced as a by-product during the reaction can be removed as an azeotrope of toluene regardless of the polymerization solvent.
[0054]
Moreover, it is desirable that the basic compound used in the above reaction acts to collect hydrogen fluoride generated to promote the reaction. Examples of such basic compounds include potassium carbonate, calcium carbonate, potassium hydroxide, calcium hydroxide, potassium fluoride, triethylamine, tributylamine, and pyridine. Under the present circumstances, the usage-amount of a basic compound is 0.1-5 mol with respect to 1 mol of PFBN used, Preferably it is 0.5-2 mol.
[0055]
Further, the reaction conditions in the above reaction are R ¹ The reaction is not particularly limited as long as the reaction between the compound represented by H and PFBN proceeds efficiently. For example, the reaction is usually 20 to 180 ° C. while preferably maintaining the reaction system in a stirred state. It is preferably carried out at a temperature of 40 to 160 ° C. Moreover, although reaction time changes with other reaction conditions, the raw material to be used, etc., it is 1-48 hours normally, Preferably it is 2-24 hours. Furthermore, the reaction may be carried out under normal pressure or under reduced pressure, but it is desirable to carry out under normal pressure from the viewpoint of equipment. The product obtained by such a reaction is obtained by adding distilled water to the reaction mixture and extracting with an extractant such as dichloromethane, dichloroethane, or carbon tetrachloride, and then separating the organic layer from the extract and distilling the extractant. It is obtained by leaving. Furthermore, if necessary, this product may be obtained as crystals by recrystallization from methanol or ethanol.
[0056]
The tetrafluorobenzonitrile derivative of the formula (2) synthesized as described above is further subjected to polymerization in the presence of a dihydroxy compound of the formula (3) and a basic catalyst as described above, and thereby the target A polycyanoaryl ether of formula (1) is prepared. At this time, the tetrafluorobenzonitrile derivative of the formula (2) may be used after being subjected to purification steps such as extraction, recrystallization, chromatography and distillation as described above, or may be used as it is without performing the purification step. However, considering the yield of the next step, etc., it is preferably used after being purified.
[0057]
The dihydroxy compound of formula (3) used in the above reaction is selected according to the structure of the polycyanoaryl ether of formula (1) which is the target product. As the dihydroxy compound of the formula (3) preferably used in the present invention, as described below, 2,2-bis (4-bidroxyphenyl) -1,1,1,3,3,3- Hexafluoropropane (hereinafter referred to as “6FBA”), 4,4′-dihydroxydiphenyl ether (hereinafter referred to as “DPE”), hydroquinone (hereinafter referred to as “HQ”), bisphenol A (hereinafter referred to as “BA”), 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter referred to as “HF”), phenolphthalein (hereinafter referred to as “PP”), 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene ( Hereinafter, referred to as “MHF”), 1,4-bis (hydroxyphenyl) cyclohexane (hereinafter referred to as “CHB”), and 4,4′-dihydro Shi biphenyl (hereinafter referred to as "BP"), and the like.
[0058]
Embedded image
[0059]
In the above reaction, the tetrafluorobenzonitrile derivative of the formula (2) and the dihydroxy compound of the formula (3) may be used as a single compound, respectively, or two or more kinds of the tetrafluorobenzonitrile derivatives of the formula (2) And / or may be used in the form of a mixture of dihydroxy compounds of the formula (3), but it is preferably used as a single compound in consideration of the purification process and the physical properties of the polymer. In the latter case, the total number of moles of the plural or single tetrafluorobenzonitrile derivatives of the formula (2) used is the sum of the number of moles of the plural or single dihydroxy compound of the formula (3). It is preferable that the amount of the dihydroxy compound of the formula (3) used is 0.1 to 5 mol with respect to 1 mol of the tetrafluorobenzonitrile derivative of the formula (2). Preferably it is 1-2 mol.
[0060]
The reaction may be performed in an organic solvent or in the absence of a solvent, but is preferably performed in an organic solvent. In the former case, usable organic solvents include, for example, polar solvents such as N-methyl-2-pyrrolidinone, N, N-dimethylacetamide, acetonitrile, benzonitrile, nitrobenzene, nitromethane, and methanol; and these polar solvents and toluene And a mixed solvent with a nonpolar solvent such as xylene. These organic solvents may be used alone or in the form of a mixture of two or more. Moreover, the density | concentration of the tetrafluoro benzonitrile derivative of Formula (2) in an organic solvent is 1-50 mass%, Preferably, it is 5-20 mass%. In this case, when toluene or other similar solvent is used in the initial stage of the reaction, water produced as a by-product during the reaction can be removed as an azeotrope of toluene regardless of the polymerization solvent.
[0061]
In the present invention, it is essential that the reaction of the tetrafluorobenzonitrile derivative of the formula (2) and the dihydroxy compound of the formula (3) is performed in the presence of a basic catalyst. The basic catalyst preferably has a function of converting the dihydroxy compound of formula (3) into a more reactive anion so as to promote the polycondensation reaction by the dihydroxy compound of formula (3). Examples thereof include potassium, calcium carbonate, potassium hydroxide, calcium hydroxide, and potassium fluoride. The amount of the basic catalyst used is not particularly limited as long as the reaction between the tetrafluorobenzonitrile derivative of formula (2) and the dihydroxy compound of formula (3) can proceed satisfactorily. The tetrafluorobenzonitrile derivative (2) is usually 0.1 to 5 mol, preferably 0.5 to 2 mol, per 1 mol.
[0062]
Furthermore, the reaction conditions in the polymerization reaction are not particularly limited as long as the reaction between the tetrafluorobenzonitrile derivative of formula (2) and the dihydroxy compound of formula (3) proceeds efficiently, The polymerization temperature is preferably 200 ° C. or lower, more preferably 20 to 150 ° C., and most preferably 40 to 100 ° C. By reacting at such a low temperature, side reactions can be suppressed and gelation of the polymer can be prevented without requiring special equipment. Moreover, although superposition | polymerization time changes with other reaction conditions, the raw material to be used, etc., Preferably it is 1-48 hours, More preferably, it is 2-24 hours. Furthermore, the polymerization reaction may be performed under normal pressure or under reduced pressure, but it is preferable to perform under normal pressure from the viewpoint of equipment.
[0063]
After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation or the like, and the distillate is washed as necessary to obtain a desired polymer. Alternatively, the polymer may be obtained by adding the reaction solution in a solvent having low polymer solubility to precipitate the polymer as a solid, and separating the precipitate by filtration.
[0064]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0065]
In the following examples, physical properties were evaluated as follows.
[0066]
The chemical structures of the monomers and polymers synthesized in the following examples are FT-IR (manufactured by JASCO Corporation, FT-IR350), and ¹ H- and ¹⁹ F-NMR (manufactured by Varian, Unity 500, operating conditions are: ¹ 500 MHz for H-NMR; and ¹⁹ Was 470 MHz in F-NMR), and CDCl _Three Was measured and confirmed as a solvent. In addition, 4,4′-difluorobenzophenone ¹⁹ Used as internal standard for F-NMR measurement.
[0067]
The measurement of the reduced viscosity was carried out in dimethylacetamide (DMAc) using an Ostwald-Fenske viscometer at a concentration of 0.5 g / 100 ml and a temperature of 25 ° C.
[0068]
The glass transition temperature (Tg) and the melting temperature (Tm) were measured using a differential scanning calorimeter (Perkin-Elmer, DSC7) at a heating rate of 20 ° C./min in a nitrogen atmosphere.
[0069]
Thermal stability was measured using a thermogravimetric apparatus (Perkin-Elmer, TGA7) at a heating rate of 20 ° C./min in a nitrogen atmosphere.
[0070]
The molecular weight was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. At this time, an NMP solution containing 10 mM / liter LiBr was used as a developing solvent, the flow rate was 0.7 ml / min, and the column temperature was 40 ° C.
[0071]
For the solubility, the sample polymer was charged in a solvent so as to have a concentration of 20% by mass, the difference in solubility was observed, and classified according to the solubility as follows. ++: dissolved at room temperature, +: partially dissolved, ±: swollen, −: insoluble.
[0072]
The film formability is such that the sample polymer is charged to a concentration of 20% by mass in toluene, and a 20% by mass toluene solution (dispersion liquid depending on the polymer) is bar-coated on the glass substrate. And the hue was observed. In addition, about the film formation property, it classified as follows. ++: excellent, +: good, ±: bad, −: extremely bad.
[0073]
Synthesis Example 1: Synthesis of 4-phenoxy-2,3,5,6-tetrafluorobenzonitrile (PtFBN)
The following reaction was performed as follows.
[0074]
Embedded image
[0075]
Specifically, a 100 ml flask equipped with a reflux tube and a Dean-Stark trap was charged with 5.0 g (53.2 mmol) phenol, 3.67 g (26.6 mmol) potassium carbonate (K ₂ CO _Three ), 60 ml N-methyl-2-pyrrolidinone (NMP) and 15 ml toluene. This mixed solution was subjected to azeotropic dehydration for 2 hours at 130 ° C. in a nitrogen stream to synthesize a phenol potassium salt. After confirming a stoichiometric amount (about 1 ml) of water, toluene was distilled off and the mixture was cooled. When the temperature of the reaction solution reached 100 ° C., 10.26 g (53.2 mmol) of 2,3,4,5,6-pentafluorobenzonitrile was added to the reaction solution, and the temperature was maintained while maintaining this temperature. Reacted for hours. After completion of the reaction, 50 ml of distilled water was added, followed by extraction with dichloromethane. Further, the organic layer was collected, washed with water, dried over sodium sulfate, and dichloromethane was distilled off to obtain a brown oily crude product.
[0076]
Next, this crude product was distilled under reduced pressure at 102 ° C./0.4 mmHg, and then recrystallized with ethanol to obtain white crystals. The yield at this time was 40%. Further, the melting temperature of the obtained product is 68 ° C., and its IR (KBr) spectrum, ¹ H-NMR (CDCl _Three ) Spectrum and ¹⁹ F-NMR (CDCl _Three ) The spectra are shown in FIG. 1, FIG. 2 and FIG. 3, respectively. In addition, ¹⁹ In the F-NMR spectrum: ¹⁹ The F chemical shift is given in ppm corresponding to 4,4′-difluorobenzophenone = −110.1 ppm.
[0077]
Example 1: Synthesis of 2F-PEN-6FBA
The following polymerization reaction was performed as follows.
[0078]
Embedded image
[0079]
Specifically, in a 25 ml flask equipped with a reflux tube and a Dean-Stark trap, 0.377 g (1.12 mmol) of 2,2-bis (4-bidoxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane (6FBA), 0.171 g (1.24 mmol) potassium carbonate, 2.5 ml N-methyl-2-pyrrolidinone (NMP) and 2.5 ml toluene Was charged. This mixed solution was subjected to azeotropic dehydration at 130 ° C. for 2 hours under a nitrogen stream to synthesize 6FBA potassium salt. After confirming a stoichiometric amount (about 0.04 ml) of water, toluene was distilled off and the mixture was allowed to cool. When the temperature of the reaction solution reached 80 ° C., 0.300 g (1.12 mmol) of PtFBN obtained in Synthesis Example 1 was added to the reaction solution and reacted for 20 hours while maintaining this temperature.
[0080]
After completion of the reaction, this solution was poured into a 1% aqueous acetic acid solution with vigorous stirring using a blender. The precipitated polymer was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure. The polymer recovered in this manner was dissolved in dimethylacetamide (DMAc) so as to have a concentration of 30 wt / vol%, and this solution was slowly poured into methanol with stirring and purified by a reprecipitation method. . After leaving to solidify completely, the precipitated and solidified polymer was filtered and dried under reduced pressure. The yield at this time was 86.0%. Moreover, the glass transition temperature of the obtained product is 163.0 degreeC, The IR (film) spectrum, ¹ H-NMR (CDCl _Three ) Spectrum and ¹⁹ F-NMR (CDCl _Three ) The spectra are shown in FIGS. 4, 5 and 6, respectively. In addition, ¹⁹ In the F-NMR spectrum: ¹⁹ The F chemical shift is given in ppm corresponding to 4,4′-difluorobenzophenone = −110.1 ppm.
[0081]
Example 2
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.358 g (1.12 mmol) of PP was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-PP was obtained as product. The yield at this time was 94.9%, and the glass transition temperature of the obtained product was 235.0 ° C.
[0082]
Example 3
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.256 g (1.12 mmol) of BA was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-BA was obtained as product. The yield at this time was 86.8%, and the glass transition temperature of the obtained product was 143.6 ° C.
[0083]
Example 4
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.394 g (1.12 mmol) of HF was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-HF was obtained as product. The yield at this time was 93.5%, and the glass transition temperature of the obtained product was 232.2 ° C.
[0084]
Example 5
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.123 g (1.12 mmol) of HQ was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-HQ was obtained as product. The yield at this time was 85.5%, and the glass transition temperature of the obtained product was 145.9 ° C.
[0085]
Example 6
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.394 g (1.12 mmol) of CHB was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-CHB was obtained as product. The yield at this time was 87.4%, and the glass transition temperature of the obtained product was 151.8 ° C.
[0086]
Example 7
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.301 g (1.12 mmol) of DPE was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-DPE was obtained as product. The yield at this time was 87.1%, and the glass transition temperature of the obtained product was 142.0 ° C.
[0087]
Example 8
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 0.209 g (1.12 mmol) of BP was used instead of 0.377 g (1.12 mmol) of 6FBA. -PEN-BP was obtained as product. The yield at this time was 90.7%, and the glass transition temperature of the obtained product was 179.4 ° C.
[0088]
Table 1 shows the reduced viscosity, molecular weight, and glass transition temperature of each product obtained in Examples 1 to 8, and Table 2 shows the thermophysical properties.
[0089]
[Table 1]
[0090]
[Table 2]
[0091]
Example 9
About the polymer obtained in Examples 1-8, when the solubility was evaluated, the result shown in Table 3 was obtained.
[0092]
[Table 3]
[0093]
Example 10
For the polymers obtained in Examples 1, 3, 5 and 7, the film forming properties were evaluated. The results shown in Table 4 were obtained.
[0094]
[Table 4]
[0095]
【Effect of the invention】
As described above, the polycyanoaryl ether of the present invention has high mechanical strength and toughness, excellent electrical properties, excellent solubility in various commonly used solvents, and heat resistance. Excellent thermal stability such as flame resistance, and excellent coating formation, so heat resistant materials, aerospace composite matrix, nuclear reactor composite matrix, electrical insulation material, electromagnetic shielding composite matrix, fuel cell Industrially versatile materials such as polymer electrolyte (separator) precursors and optical materials such as waveguides.
[0096]
In addition, the polycyanoaryl ether of the present invention can be easily and efficiently produced without requiring special equipment by subjecting the tetrafluorobenzonitrile derivative to a copolycondensation reaction with a dihydroxy compound.
[Brief description of the drawings]
1 is an IR spectrum of PtFBN obtained in Synthesis Example 1. FIG.
FIG. 2 shows PtFBN obtained in Synthesis Example 1. ¹ It is a 1 H-NMR spectrum.
FIG. 3 shows PtFBN obtained in Synthesis Example 1. ¹⁹ It is a F-NMR spectrum.
4 is an IR spectrum of 2F-PEN-6FBA obtained in Example 1. FIG.
FIG. 5 shows the 2F-PEN-6FBA obtained in Example 1. ¹ It is a 1 H-NMR spectrum.
FIG. 6 shows the 2F-PEN-6FBA obtained in Example 1. ¹⁹ It is a F-NMR spectrum.

Claims (4)

Following formula (1):
Where R ¹ is phenoxy, phenylthio, or anilino ; R ² is represented by the following formula:
Divalent any organic based represent represented in; and n is the degree of polymerization and Table Wa is 5 to 1000, in polycyanoaryl ether represented. The polycyanoaryl ether according to claim ¹ , wherein R ¹ is phenoxy in the formula (1). Following formula (2):
However, R ¹ is a tetrafluorobenzonitrile derivative represented by the following formula (3): phenoxy, phenylthio, or anilino
However, ^{R 2} is represented by the following formula:
A process for producing a polycyanoaryl ether according to claim 1 or 2 , comprising polymerizing in the presence of a basic catalyst and a dihydroxy compound represented by any one of the divalent organic groups represented by: The method according to claim 3, wherein the polymerization of the tetrafluorobenzonitrile derivative and the dihydroxy compound is performed at a temperature of 150 ° C or lower.